CN106349730A - Resin composition and molded article using the same - Google Patents
Resin composition and molded article using the same Download PDFInfo
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- CN106349730A CN106349730A CN201511019681.7A CN201511019681A CN106349730A CN 106349730 A CN106349730 A CN 106349730A CN 201511019681 A CN201511019681 A CN 201511019681A CN 106349730 A CN106349730 A CN 106349730A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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Abstract
Disclosed are a resin composition and a molded article using the same. The resin composition may be obtained by mixing a thermoplastic vulcanizate and a polyethylene resin with a thermoplastic olefin resin, a polypropylene resin, an inorganic filler and a thermoplastic rubber, and in particular, the thermoplastic vulcanizate and the polyethylene resin may be obtained from biologically obtainable materials (biomass). Thus, the resin composition may be environmentally-friendly because it does not emit offensive odor of harmful compounds due to decreased generation of carbon dioxide and volatile organic compounds unlike petroleum-based materials. Further, superior mechanical properties such as elongation, hardness, strength, etc. that cannot be achieved only with conventional biodegradable resin may be ensured, and, at the same time, processability and moldability may be improved.
Description
Technical field
The present invention relates to resin combination and the mechanograph using this resin combination.Resin combination
Thing can by by TPV and polyvinyl resin and thermoplastic olefin resin, poly- third
Olefine resin, inorganic filler and thermoplastic elastomer mix and obtain, specifically, thermoplastic vulcanizates rubber
Glue and polyvinyl resin can obtain from biomaterial.So, resin combination is environmental protection,
Because it is contrary with petroleum-type material, can be because reducing carbon dioxide and VOC
Generation and do not give out the bad smell of hazardous compound.Furthermore, it is possible to guarantee only using
The excellent mechanical property that cannot realize during standard biologic degradable resin such as elongation percentage, hardness,
Intensity etc., and machinability and moldability can be improved simultaneously.
Background technology
Including polyvinyl resin, acrylic resin, Corvic, acrylic resin, phenol
The synthetic resin of resin etc. is generally and be widely used in daily life.For example, containing such conjunction
The compositionss of resin due to excellent moldability, impact resistance, chemical resistance, low-gravity and
Low cost has been widely used in moulded goods and the inner/outer part of vehicle.
However, being probably environmentally undesirable by sheet material prepared by synthetic resin, because in its preparation
During cause environmental pollution, and it cannot recycle after a procedure.In addition, petroleum base
Synthetic resin is harmful to environment and human body, because it produces volatile organic compound in higher concentrations
Thing, this can produce secondary pollution by the photochemical reaction in atmospheric environment, such as photochemistry
Oxide.
In the prior art, Korean Patent Publication No. 2012-0047113 disclose by using
Plastics and the method for preparing this plastics that agricultural residue is prepared as raw material, to circulate
Using waste resource and reduce production cost.However, the plastics producing are likely to be of and make us discontented
The mechanical property of meaning.
Additionally, Korea patent registration the 091016th discloses and carries out copolymerization containing ethylene and propylene
The compositionss of the vistanex obtaining.However, problem of environmental pollution possibly cannot fully solve,
Because it contains common polyvinyl resin and vistanex.
In addition, Korean Patent Publication No. 2009-0131843 discloses polypropylene/soy-protein again
Condensation material compositionss, the biological composite sheet using said composition and for preparing said composition
Method.However, because soybean protein can directly use, product quality may be with Semen sojae atricolor egg
White quality and change.
Therefore, it is necessary to developing synthetic resin can be substituted and reduces environmental pollution and distribute simultaneously
Go out the novel environment friendly resin material of less VOC and use this novel environment friendly resin
The product of material.
Content of the invention
At preferred aspect, the present invention provides a kind of resin combination, and it is by making thermoplasticity sulfur
Change rubber and polyvinyl resin and thermoplastic olefin resin, acrylic resin, inorganic filler and heat
Plastic rubber mixes and obtains, and specifically, TPV and polyvinyl resin can wrap
Include biology and can obtain component, or can obtain component from biology or obtain from biomass.So,
Resin combination is environmental protection because it is unlike petroleum-type material, due to reduce carbon dioxide and
The generation of VOC and do not distribute the bad smell of hazardous compound it is possible to really
Protect the excellent mechanical property that cannot realize when only using standard biologic degradable resin such as to prolong
Stretch rate, hardness, intensity etc., machinability and moldability can be improved simultaneously.
Therefore, the present invention provides a kind of environment-friendly resin compositionss, and it produces less carbon dioxide
And VOC.
The present invention also provides a kind of machinability showing improvement and moldability and by mechanical property
Guarantee the mechanograph on certain level.
Additionally, the present invention provides a kind of method for preparing mechanograph, this mechanograph can lead to
Cross recycling and be reused in other purposes.
In one aspect, the present invention provides a kind of resin combination, and it can comprise: amount is about
The TPV of 10wt% to 40wt%；Amount is the poly- second of about 20wt% to 30wt%
Olefine resin；Amount is the thermoplastic olefin resin of about 30wt% to 50wt%；Amount be about 1wt% extremely
The acrylic resin of 10wt%；And measure be about 1wt% to 10wt% inorganic filler, own
Wt% is based on the gross weight of resin combination.Specifically, TPV and polyethylene tree
Fat can be respectively since biomass obtain.
Terms used herein " biomass " refers to that biology can obtain material or from work or dead
The component of organism, and " biology can obtain material " refer to biomaterial or from organism generate,
The material producing, synthesizing, drain and/or process.In some aspects, biomass can be specifically
Refer to biology and can obtain material or the component from plant or animal, including the material from plant and animal
Material, its purpose that generally may be not used in food or feed the mankind or domestic animal.For example, biomass
Can include polytype plant, crops, forest residues such as be derived from plant timber,
Branch, dry fibers, from the solid waste of animal, and the fragment from organism, it can
To be directly or indirectly transformed into resource such as material or energy by means of biological or chemical method
(fuel).Exempla bibiomass mentioned by herein can include from such as Semen Maydiss, arithoke,
The material of Caulis Sacchari sinensis, Radix Betae etc..
Preferably, TPV can comprise all to obtain oil or the EPDM of authigenic material
Rubber (epdm) or its mixture.Additionally, polyvinyl resin can by making vinyl polymerization and
Obtain, this ethylene is prepared by the dehydration of the ethanol obtaining authigenic material.Specifically, it is used for
The ethanol of polyvinyl resin can be from selected from one of Semen Maydiss, arithoke, Caulis Sacchari sinensis and Radix Betae or many
Plant and extract.
Preferably, thermoplastic olefin resin may be in fully crosslinked, half crosslinking and non-crosslinked
At least one state.
Preferably, thermoplastic olefin resin can be selected from polyethylene, polypropylene, polyamide,
Merlon, polystyrene, styrene-acrylonitrile (san), acrylonitrile-butadiene-styrene (ABS)
And one or more of poly- (methyl methacrylate) (pmma) (abs).
Preferably, acrylic resin is sym-propene polymer resin.Specifically, acrylic resin is permissible
Have 30,000 to 40,000 number-average molecular weight (mn) and 25g/10 minute to 40g/10
The melt index (230 DEG C, 2.16kg) of minute.
Preferably, inorganic filler can be in Calcium Carbonate, calcium oxide, Muscovitum and Talcum
One or more.
Resin combination can also comprise based on the amount of resin combination gross weight be about 1wt% extremely
The thermoplastic elastomer of 20wt%.Preferably, thermoplastic elastomer can be total based on thermoplastic elastomer
The amount of weight is the ethylene of about 50wt% to 60wt% with to measure be about 40wt% to 50wt%
c2-c10The copolymer of alhpa olefin.Specifically, c2-c10Alhpa olefin can be selected from propylene, butylene,
One or more of amylene, hexene and octene.In addition, thermoplastic elastomer can be selected from second
Third rubber (epr), ethylene propylene diene rubber (epdm), ethylene butylene rubber (ebr) and
One or more of Ethylene-octene rubber (eor).
Additionally, it is provided resin combination that is being made up of said components or being consisting essentially of.Example
As resin combination can be composed of the following components or substantially composed of the following components: amount is about
The TPV of 10wt% to 40wt%；Amount is the poly- second of about 20wt% to 30wt%
Olefine resin；Amount is the thermoplastic olefin resin of about 30wt% to 50wt%；Amount be about 1wt% extremely
The acrylic resin of 10wt%；And measure be about 1wt% to 10wt% inorganic filler, own
Wt% is based on the gross weight of resin combination.
In yet another aspect, the present invention provides the mechanograph using above-mentioned resin combination preparation.
In yet another aspect, the present invention is provided to the method preparing mechanograph, the method is permissible
Comprise the following steps: the biological thermoplastic vulcanizates rubber being about 10wt% to 40wt% by combined amount
Glue, to measure be the biological polyethylene resin of about 20wt% to 30wt%, to measure be about 30wt% to 50
The thermoplastic olefin resin of wt%, measure be about 1wt% to 10wt% acrylic resin and
Amount be the inorganic filler of about 1wt% to 10wt% preparing mixture, all wt% are based on this
The gross weight of mixture；And prepare mechanograph by melting this mixture.Specifically, such as
Described in upper, TPV and polyvinyl resin respectively since biomass obtain, or can wrap
Containing biological available component.
Also provide vehicle, it comprises the mechanograph using the preparation of above-mentioned resin combination.
Resin combination according to the present invention can comprise to may each comprise the thermoplastic that biology can obtain component
Property vulcanite and polyvinyl resin, therefore, resin combination can be environmental protection, because its
Unlike petroleum-type material, due to reducing carbon dioxide and VOC (voc)
Generate and do not distribute the bad smell of hazardous compound, and can be circulated by recycling
For other purposes.Additionally, this resin combination may insure only using currently used life
The excellent mechanical property that cannot realize during Biodegradable resin such as elongation percentage, hardness, intensity
Deng, thus machinability and moldability can be improved simultaneously.
Additionally, because the resin combination of the present invention can have in terms of cost competitiveness and sense of touch
Advantageous, using the mechanograph of this resin combination can be used for vehicle inner/outer part,
Flooring product, decorative panel, film etc..
Specific embodiment
It should be understood that terms used herein " vehicle " or " vehicle " or other similar terms
Including common motor vehicles, it may for example comprise Multifunctional bicycle (suv), bus, card
Car, the passenger vehicle of various commercial vehicle, including the water carrier of various ships and ship, aircraft etc.
Deng, and include hybrid electric vehicle, electric motor car, plug-in hybrid electric vehicles, hydrogen-powered vehicle and
Other substitute fuel cars (for example, the fuel of the resource beyond oil).Referred to herein
Hybrid electric vehicle be the car with two or more power resources, for example simultaneously for gasoline move
Power and electrodynamic car.
Terms used herein only illustrates specific embodiment, rather than is intended to limit the present invention.
" one, a kind of, should " be also intended to including plural form as it is used herein, singulative,
Unless clearly dictated otherwise in context.It is to be further understood that the art using in the description
Language " include, comprise, containing " refers to there is described feature, integer, step, operation, unit
Element and/or part, but do not preclude the presence or addition of other features one or more, integer, step
Suddenly, operation, element, part and/or its group.As it is used herein, term "and/or"
Any and all combination listd including one or more correlations.
Clearly obtain unless otherwise indicated or from context, terms used herein " about " should be managed
Solution is in the normal tolerance of this area, such as in 2 standard deviations of average." about "
Can be understood as described value 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%,
1%th, in 0.5%, 0.1%, 0.05% or 0.01%.Unless in addition clearly drawn from context,
All numerical value provided herein is all modified by term " about ".
Hereinafter, the illustrative embodiments of the present invention will be described in further detail.
The present invention provides a kind of resin combination, and it can comprise: amount is about 10wt% to 40
The TPV (biological tpv) of wt%；Amount is the poly- second of about 20wt% to 30wt%
Alkene (biological pe) resin；Amount is the thermoplastic olefin (tpo) of about 30wt% to 50wt%
Resin；Amount is polypropylene (pp) resin of about 1wt% to 10wt%；And to measure be about 1wt%
To the inorganic filler of 10wt%, all wt% are based on the gross weight of resin combination.
In an exemplary embodiment of the present invention embodiment, resin combination is specifically using thermoplasticity sulfur
Change rubber and polyvinyl resin, both all can obtain from biomass.Additionally, resin combination
Thing can be environmental protection, because it is unlike petroleum-type material, due to reducing carbon dioxide and volatilization
The generation of property organic compound (voc) and do not distribute the bad smell of hazardous compound, and
Can be circulated for other purposes by recycling.Specifically, compared in conventional oil
Base polythene material gives out carbon dioxide when producing, and the polyvinyl resin of the present invention can be by gathering
Close bio-ethanol and be obtained, wherein bio-ethanol obtains from Caulis Sacchari sinensis etc., thus reduce carbon dioxide
Generation.
Bio-ethanol as used herein refers to all by modern biotechnology technique in other common alcohol
The biology producing as fermentation can obtain ethanol.
The resin combination of the present invention can by by TPV and polyvinyl resin with
Thermoplastic olefin resin, acrylic resin, inorganic filler and thermoplastic elastomer mix and obtain.
Specifically, TPV and polyvinyl resin obtain from biomass or biomaterial.From
And, resin combination is able to ensure that cannot be realized when only using existing biodegradable resin
Excellent mechanical property elongation percentage, hardness, intensity etc., and can improve simultaneously can plus
Work and moldability.
Detailed description according in the resin combination of the present invention each component is provided below.
1. TPV (biological TPV (biological tpv))
In an exemplary embodiment of the present invention embodiment, TPV can obtain from biomass
Arrive, and, for example can comprise all to obtain oil or the ethylene propylene diene rubber (epdm) of authigenic material
Or its mixture.Specifically, TPV can be by including adding polypropylene
To biological available oil or vegetable oil such as Petiolus Trachycarpi oil, biological available epdm or its mixing
In thing, and a kind of TPV then carrying out crosslinked step and preparing.
In an exemplary embodiment of the present invention embodiment, TPV can be based on resin group
The gross weight of compound, is used with the amount of about 10wt% to 40wt%.When its content is below about 10
During wt%, due to physical characteristics unsatisfactory such as intensity (tensile strength or tearing strength),
Elongation percentage etc. is it may be difficult to be prepared into mechanograph.And, as its content greater than about 40wt%,
Processing cost may increase.
2. polyvinyl resin (biological polyethylene (biological pe) resin)
In an exemplary embodiment of the present invention embodiment, polyvinyl resin can be by include make by
A kind of poly- second obtained from step that the ethylene that biology can obtain the dehydration of ethanol and prepare is polymerized
Olefine resin.Ethanol can obtain as biomass sources from plant.For example, liquid fuel,
Methanol, ethanol, diesel oil etc. biology can be able to be obtained by processing biological.Specifically,
Ethanol used in polyvinyl resin can be from selected from Semen Maydiss, arithoke, Caulis Sacchari sinensis and Radix Betae
One or more in extract a kind of ethanol.For example, ethanol can be by from Caulis Sacchari sinensis or Radix Betae
Middle extracting directly sugar simultaneously and then carries out alcoholic fermentation and obtains.
In an exemplary embodiment of the present invention embodiment, polyvinyl resin can be with about 20wt% to 30
The amount of wt% uses.When its content is below about 20wt%, machinability and moldability may make
People is unsatisfied with.And, as its content greater than about 30wt%, processing cost may increase.
3. thermoplastic olefin (tpo) resin
In an exemplary embodiment of the present invention embodiment, thermoplastic olefin resin can be added, to carry
For having the resin combination of melt strength and sufficient flow during vacuum mo(u)lding, and can
To be used with least one state in fully crosslinked, half crosslinking and non-crosslinked.Specifically,
Thermoplastic olefin resin under fully crosslinked state can be used for the extension preventing resin combination
Rate excessively increases, and for preventing the decline of pruning property after molding.
Additionally, the structure that the thermoplastic olefin resin under half cross-linked state can have is, gather
Propylene chain can run through the resin under half cross-linked state, and when it extends through external force, permissible
Reduce the thickness deviation of compositionss by making resin combination uniform extension.
Additionally, the thermoplastic olefin resin under uncrosslinked state can have than fully crosslinked shape
The low melt strength of thermoplastic olefin resin under state or under half cross-linked state, but can have
The melt strength higher than general olefin resin.Thermoplastic olefin tree under using uncrosslinked state
During fat, EP rubbers (epr) can serve as the thermoplastic elastomer that can add together.In this feelings
Under condition, this is favourable, and the VOC with bad smell will not produce, and
And the appearance that has almost no change in physical characteristics, because not using cross-linking agent.
In an exemplary embodiment of the present invention embodiment, thermoplastic olefin resin can be selected from poly- second
Alkene, polypropylene, polyamide, Merlon, polystyrene, styrene-acrylonitrile (san),
In acrylonitrile-butadiene-styrene (ABS) (abs) and poly- (methyl methacrylate) (pmma)
One or more.
In an exemplary embodiment of the present invention embodiment, thermoplastic olefin resin can be based on resin group
Compound gross weight, is used with the amount of about 30wt% to 50wt%.When its content is below about 30wt%
When, due to the intensity decreases of resin combination, roll processability and moldability is possibly made us not
Satisfied.And, as its content greater than about 30wt%, resin combination may give out and wave
The bad smell of the property sent out organic compound.
4. polypropylene (pp) resin
In an exemplary embodiment of the present invention embodiment, acrylic resin can be added, by tree
Oil/fat composition provides rigidity to improve the ability keeping shape, and can use known in the art
Any resin and unrestricted.Specifically, it is possible to use be only made up of acrylic resin is equal
Poly- type polypropylene, it gives out the bad smell of less VOC, and warp
Go through and less respond to temperature or the change of light.
Acrylic resin can have about 30,000 to 40,000 number-average molecular weight (mn) and
About 25g/10 minute is molten to 40g/10 minute (in about 230 DEG C of temperature, under about 2.16kg)
Melt index.Specifically, acrylic resin can be have about 0.89 to 0.91 proportion, about 90
Shore a hardness to 97 and about 20% to 30% elongation percentage with reduce resin Composition increase
A kind of acrylic resin of elongation percentage.
In an exemplary embodiment of the present invention embodiment, acrylic resin can be based on resin combination
Gross weight, used with the amount of about 1wt% to 10wt%.When its content is below about 1wt%,
Moldability during processing is possibly unsatisfactory, because the melting of resin combination is strong
Degree rapid decrease, and during vacuum mo(u)lding due to resin combination hardening and it may happen that
Explosion.In addition, mechanograph prepared therefrom is likely to be of texture unsatisfactory.And,
As content greater than about 10wt%, mechanograph prepared therefrom is likely to be of unsatisfactory outer
Appearance quality.
5. inorganic filler
In an exemplary embodiment of the present invention embodiment, inorganic filler can be used for improving resin combination
The mechanical property of thing, and can be in Calcium Carbonate, calcium oxide, Muscovitum and Talcum one
Plant or multiple.
In an exemplary embodiment of the present invention embodiment, inorganic filler can be based on resin combination
Gross weight, is used with the amount of about 1wt% to 10wt%.When its content is below about 1wt%,
The mechanical property of resin combination is possibly unsatisfactory, and compositionss may be tacky.
And, as its content greater than about 10wt%, increase because of compositionss during molding
Hardness and reduce elongation percentage and the explosion of resin combination occurs.Specifically, inorganic filler can
To be to there is about 2.6 proportion and mould to for vehicle interior part according in automobile industry
Expect that the abnormal smells from the patient evaluation criteria of product is a kind of inorganic filler of class 4 or greater degree.
6. thermoplastic elastomer
In an exemplary embodiment of the present invention embodiment, resin combination can also comprise based on resin
The amount of composition total weight is the thermoplastic elastomer of about 1wt% to 20wt%.Specifically, permissible
Add thermoplastic elastomer to improve the impact resistance of resin combination, and can be using based on heat
The amount of plastic rubber gross weight be about 50wt% to 60wt% ethylene with based on thermoplastic elastomer
The amount of gross weight is the c of about 40wt% to 50wt%2-c10The copolymer of alhpa olefin.Work as c2-c10α
When the content of alkene is below about 40wt%, the machinability of resin combination possibly makes us discontented
Meaning.And, as its content greater than about 50wt% although surface tactile sensation is because under compositionss
Fall hardness and be improved, calendering processability possibly unsatisfactory.
In an exemplary embodiment of the present invention embodiment, c2-c10Alhpa olefin can be in prior art
Any c knowing2-c10Alhpa olefin, and unrestricted.Specifically, it is possible to use selected from propylene, fourth
One or more of alkene, amylene, hexene and octane.
In an exemplary embodiment of the present invention embodiment, thermoplastic elastomer can be selected from EP rubbers
(epr), ethylene propylene diene rubber (epdm), ethylene butylene rubber (ebr) and ethylene-pungent
One or more of alkene rubber (eor).Preferably, it is possible to use Ethylene-octene rubber
(eor).
Specifically, Ethylene-octene rubber (eor) can be comprised and be added to resin combination to overcome
The shortcoming of the thermoplastic olefin of thing, such as low-intensity and the volatile organic with bad smell
Compound.Ethylene-octene rubber can be provided and thermoplasticity to resin combination together with inorganic filler
The similar melt strength of olefin resin, and improve the abnormal smells from the patient of compositionss.
The grade of Ethylene-octene rubber (eor) is classified generally according to its octene content.Pungent
Alkene content can be the about 40wt% to 50wt% based on Ethylene-octene rubber weight, or especially
Ground is about 40wt% to 45wt%.
In an exemplary embodiment of the present invention embodiment, thermoplastic elastomer can be with about 1wt% to 20
The amount of wt% uses.When its content is below about 1wt%, during vacuum mo(u)lding, due to resin
The melt strength of compositionss declines, and is likely to occur excessive sagging in the molded part, thus leading to
Fold in molded article surface.And, as content greater than about 20wt%, resin combination can
The bad smell of VOC can be given out.
In yet another aspect, the present invention also provides the mechanograph using the preparation of above-mentioned resin combination,
This resin combination comprises biological available component.
The method for preparing mechanograph of the present invention may comprise steps of: by combined amount
It is the TPV of about 10wt% to 40wt%, to measure be about 20wt% to 30wt%
Polyvinyl resin, to measure be the thermoplastic olefin resin of about 30wt% to 50wt%, to measure be about 1wt%
To the acrylic resin of 10wt% and to measure be that the inorganic filler of about 1wt% to 10wt% to be made
Standby mixture, all wt% are based on the gross weight of this mixture；And by melting this mixing
Thing is preparing mechanograph.Specifically, TPV and polyvinyl resin can each wrap
Component can be obtained containing biology or component can be obtained from biology and obtain.
In an exemplary embodiment of the present invention embodiment, mechanograph can be mixed by making thus prepare
Polymer melt is simultaneously passed to stack and is prepared.The melting of mixture can be according to conventional
Method is held using single screw extrusion machine, double screw extruder, kneader or Banbury mixer
OK, but can be not limited to this.And, roll can according in art of the present invention
The common methods known are executing.
Therefore, according to the present invention comprise all be available from biology and can obtain the thermoplastic vulcanizates rubber of component
The resin combination of glue and polyvinyl resin can be environmental protection, because it is unlike petroleum-type material,
Do not distribute harmful due to reducing the generation of carbon dioxide and VOC (voc)
The bad smell of compound, and other purposes can be recycling in by recycling.
In addition, by by TPV and polyvinyl resin and thermoplastic olefin resin,
The resin combination of the present invention that acrylic resin, inorganic filler and thermoplastic elastomer mix and obtain
Thing is it can be ensured that the excellent machinery that cannot realize when only using existing biodegradable resin
Characteristic elongation percentage, hardness, intensity etc., and machinability and molding can be improved simultaneously
Property.
Additionally, because the resin combination of the present invention can have in terms of cost competitiveness and sense of touch
Advantageous, using the mechanograph of this resin combination can be used for vehicle inner/outer part,
Flooring product, decorative panel, film etc..Specifically, mechanograph can be prepared into sheet material, film etc.,
Inner body/exterior part for vehicle.Because mechanograph has excellent physical characteristics,
Solvent resistance, wearability, Scratch Resistance, light resistance, thermostability, chemical resistance etc.,
And it is environmental protection, it can be used for the surfacing of vehicle interior part, to improve in vehicle
Atmosphere and do not give out bad smell.
Embodiment
The present invention will be described bright in more detail by embodiment.Following examples merely for
The purpose that illustrates, and to those skilled in the art it is apparent that the present invention
Scope is not restricted to these embodiments.
Embodiment 1～3 and comparative example 1～3
Prepare resin combination with the composition components described in table 1 and content.By each resin
Compositionss melt, and are pressed into piece between the rolls, and and then calendering obtains sheet material.
Table 1
Test case 1: the assessment of physical characteristics
In embodiment 1～3 and comparative example 1～3, the physical characteristics of the sheet material of preparation pass through following sides
Method and measure.Result is given in table 3 below.
[appraisal procedure]
(1) tensile strength and elongation percentage
According to astm d 638, measure tensile strength and elongation percentage using cupping machine.?
The reference dot spacing of the test speed of 200mm/ minute and 70mm under conditions of, using i
The original units of measurement of type test specimens gives peak load and the elongation percentage of area.
(2) tearing strength
According to ks m6518, under the conditions of the draw speed of 200mm/ minute, by by dumbbell
Type b test sample is clamped to cupping machine, and tearing strength is measured as load mean value.
(3) heat-resistant aging
By test sample is placed on 300 in the forced convertion heating furnace remain 110 ± 2 DEG C
Hour, and determine the △ ecmc in 45° angle using spectrophotometer, and according in iso
Specified in 105-a02, tonal gradation with the naked eye assesses color change, thus measuring heat-proof aging
Property.
(4) light fastness aging
By in 89 ± 3 DEG C of Black panel temperature, the controlled humidity of 50 ± 5%rh and 126
mj/m2Under conditions of, using in tester specified in iso 105 to test sample irradiation light,
And tonal gradation according to specified in iso 105-a02 with the naked eye assesses color change, thus
Measurement light fastness aging.
(5) chemical resistance
By the gauze with being sufficiently impregnated with listed test solution in table 2 below come to test
Sample surface wipes 10 times so that it stands 1 hour at room temperature, and according in iso
Specified in 105-a02, tonal gradation with the naked eye assesses color change, thus measuring chemical resistance.
Table 2
| Test solution | Explanation |
| Glass cleaner | Alkalescence glass cleaner |
| Cleaning agent | 95% distilled water and the mixture of 5% neutral detergent |
| Detergent | 50% isopropanol and the mixture of 50% distilled water |
| Gasoline | Lead-free gasoline |
| Buffing wax | hmc |
(6) resistance to sunscreen cream
According to gmn 10033 by the byssuss of two panels formed objects are stacked on aluminium sheet (50
Mm × 50mm) on, and over its entire surface coating 0.25g sunscreen cream (coppertone,
Water baby, spf 45), thus measuring resistance to sunscreen cream.Test sample is being placed on aluminium sheet
And after being pressed with the load of 500g, assembly is stood 1 hour in 80 ± 2 DEG C of constant temperature bath.
After removing white cotton and aluminium sheet, test sample is stood at room temperature about 10 to 15 points
Clock, is washed with neutral detergent and is dried.Then, with the naked eye assess color change.Work as color
When having almost no change, being evaluated as of making is excellent, when color somewhat changes, is evaluated as
Well, when color changes but quality does not decline, it is evaluated as medium, and works as color
When changing serious, it is poor to be evaluated as.
(7) abnormal smells from the patient of VOC
4-l glass container is heated about 1 hour at 100 DEG C and stands 1 hour at room temperature, with
Remove the abnormal smells from the patient in glass container.The test sample being cut into 50mm × 60mm size is in glass
Heat 2 hours in 100 DEG C in container.By standing 60 minutes under room temperature (23 ± 2 DEG C)
After cooling, assess abnormal smells from the patient after container cover is opened about 3cm to 4cm.By when abnormal smells from the patient tight
Distribute 5 points during weight, distribute 3 points when abnormal smells from the patient is medium, distribute 1 point when almost there is no abnormal smells from the patient
Carry out the intensity of quantitative abnormal smells from the patient.
(8) roll processability
By molten resin compositionss, by its between roller tabletted and and then calendared sheet and
After preparing sheet material, with the naked eye assessment machinability and apparent condition.When the resin group not melted
Divide residual from the teeth outwards or due to not satisfied mobility during rough surface, that makes comments
Estimate for difference, and when not having problems, being evaluated as of making is good.
(9) vacuum/injection-molding
Assessment carried out rolling, be surface-treated and lamination treatment molded sheet in vacuum mo(u)lding
Whether there is problem of appearance with during injection.The sagging being caused by the difference of resin melting intensity
Property different, cause the unexpected reduction of the explosion of molded sheet and thickness during vacuum mo(u)lding.When
When the thickness of Partial security air bag (pab) is 0.60mm or bigger, moldability is evaluated as good
Good.
(10) cohesive with injecting resin
The cohesive of assessment and injecting resin after vacuum mo(u)lding.If working as molded sheet is entered
Row is not peeling-off when forcing to peel off, then cohesive is evaluated as well, in the event of peeling off, then
It is evaluated as poor.
Table 3
From table 3 it was determined that compared with comparative example 1～3, embodiment 1～3 shows and significantly changes
Kind physical characteristics, specially tensile strength, tearing strength and elongation percentage.They also meet use
Physical characteristics in mechanograph require, and such as machinability, moldability and reliability are (heat-resisting old
The property changed, light fastness aging, chemical resistance, resistance to sunscreen cream and abnormal smells from the patient).Therefore, it can confirm,
When preparing mechanograph using said composition, it is not in the particular problem about characteristic.
On the contrary, do not comprise the TPV of authigenic material and polyvinyl resin comparison
Example 1 shows poor mechanical property, specially tensile strength, tearing strength and elongation percentage.
And, the comparative example 2 comprising a small amount of polyvinyl resin shows excessively poor mechanical property
Such as tensile strength, tearing strength and elongation percentage, excessively poor giving forth fragrance, in calendering process
Period shows poor apparent condition due to the formation of non-puddle, and shows relatively
The moldability of difference, the wherein flow due to declining during vacuum mo(u)lding, Partial security air bag
Thickness be 0.60mm or lower.
For the comparative example 3 being excessively used polyvinyl resin although calendering processability is good, because
Occur variable color, light fastness aging and heat-resistant aging poor, and vacuum/injection-molding and with
The cohesive of injecting resin is also poor.
Therefore, it can confirm, in embodiment 1～3, the resin combination of preparation shows preferably
Mechanical property, and vacuum mo(u)lding and be molded and keep prolonging pressure processability can be carried out.
Test case 2: the assessment of total volatile organic compound (tvoc) concentration
Organic for the total volatility of the sheet material measurement of preparation in embodiment 1～3 and comparative example 1
Compound and the concentration of single VOC.Result illustrates in table 4.
[method and evaluation criteria]
For embodiment 1～3 and comparative example 1～3, measure total volatile organic compound (tvoc)
Concentration.The concentration of total volatile organic compound refers to there is in the air by generally measurement
The concentration of all VOCs and the value that obtains because being not easy individually quantitative
Their concentration.
Indoor Air Quality standards by the clause 7-2 suggestion of industrial safety health bill are 500
μg/m3Or lower total volatile organic compound (tvoc), 30 μ g/m3Or lower benzene,
1000μg/m3Or lower toluene, 360 μ g/m3Or lower ethylbenzene, 700 μ g/m3Or it is lower
Dimethylbenzene, 300 μ g/m3Or lower styrene and 210 μ g/m3Or lower formaldehyde.
Table 4
As seen from Table 4, embodiment 1～3 is not only in total VOC (tvoc)
Aspect and all of VOC (voc) such as benzene, toluene, ethylbenzene,
Dimethylbenzene and styrene aspect meet the recommended standard of IAQ (indoor air quality).
On the contrary, comparative example 1 is organic in total VOC (tvoc) and volatility
Compound (voc) such as benzene, toluene, ethylbenzene, dimethylbenzene and styrene aspect are unsatisfactory for room
The recommended standard of interior air quality.In addition, it could be seen that because being included in resin combination
Concentration very high, harmful VOC is dispersed into air with very high concentration
In.
Thus, it will be seen that the embodiment 1～3 containing TPV and polyvinyl resin
It is environmental protection, because it is compared with the comparative example 1 containing Low Density Polyethylene (ldpe) resin,
Due to reducing the generation of VOC, do not give out the bad smell of hazardous compound.
As described above, the resin combination of the present invention can pass through TPV and gather
Vinyl is mixed with thermoplastic olefin resin, acrylic resin, inorganic filler and thermoplastic elastomer
Close and obtain, and specifically, TPV and polyvinyl resin can comprise biology
Component can be obtained or component can be obtained from biology and obtain.Therefore, resin combination is able to ensure that only makes
The excellent mechanical property that cannot realize during with currently used biodegradable resin such as extends
Rate, hardness, intensity etc., and machinability and moldability can be improved simultaneously.
Claims (19)
1. a kind of resin combination, it comprises:
Measure the TPV for 10wt% to 40wt%；
Measure the polyvinyl resin for 20wt% to 30wt%；
Measure the thermoplastic olefin resin for 30wt% to 50wt%；
Measure the acrylic resin for 1wt% to 10wt%；And
Measure the inorganic filler for 1wt% to 10wt%,
All wt% are based on the gross weight of described resin combination,
Described TPV and described polyvinyl resin each can obtain from biomass.
2. resin combination according to claim 1, wherein, described thermoplastic vulcanizates rubber
Glue comprises all to obtain oil or ethylene propylene diene rubber or its mixture of authigenic material.
3. resin combination according to claim 1, wherein, described polyvinyl resin leads to
Crossing makes vinyl polymerization and obtains, described ethylene by the dehydration of ethanol of authigenic material and be obtained.
4. resin combination according to claim 3, wherein, described ethanol extraction is free
From one or more of Semen Maydiss, arithoke, Caulis Sacchari sinensis and Radix Betae.
5. resin combination according to claim 1, wherein, described thermoplastic olefin tree
Fat is at least one state in fully crosslinked, half crosslinking and non-crosslinked.
6. resin combination according to claim 1, wherein, described thermoplastic olefin tree
Fat is selected from polyethylene, polypropylene, polyamide, Merlon, polystyrene, styrene-the third
One or more of alkene nitrile, acrylonitrile-butadiene-styrene (ABS) and poly- (methyl methacrylate).
7. resin combination according to claim 1, wherein, described acrylic resin is
Sym-propene polymer resin.
8. resin combination according to claim 1, wherein, described acrylic resin
Number-average molecular weight is 30,000 to 40,000, and melt index is 25 under 230 DEG C, 2.16kg
G/10min to 40g/10min.
9. resin combination according to claim 1, wherein, described inorganic filler is choosing
From one or more of Calcium Carbonate, calcium oxide, Muscovitum and Talcum.
10. resin combination according to claim 1, wherein, described resin combination
Also the amount of comprising is the thermoplastic elastomer of 1wt% to 20wt%.
11. resin combinations according to claim 10, wherein, described thermoplastic elastomer
The amount of being is the ethylene of 50wt% to 60wt% and the c measuring as 40wt% to 50wt%2-c10α alkene
The copolymer of hydrocarbon, wt% is based on the gross weight of described thermoplastic elastomer.
12. resin combinations according to claim 11, wherein, described c2-c10α alkene
Hydrocarbon is selected from one or more of propylene, butylene, amylene, hexene and octene.
13. resin combinations according to claim 10, wherein, described thermoplastic elastomer
It is in EP rubbers, ethylene propylene diene rubber, ethylene butylene rubber and Ethylene-octene rubber
One or more.
14. resin combinations according to claim 1, it is made up of following components substantially:
Measure the TPV for 10wt% to 40wt%；
Measure the polyvinyl resin for 20wt% to 30wt%；
Measure the thermoplastic olefin resin for 30wt% to 50wt%；
Measure the acrylic resin for 1wt% to 10wt%；And
Measure the inorganic filler for 1wt% to 10wt%,
All wt% are based on the gross weight of described resin combination.
15. resin combinations according to claim 1, it is made up of following components:
Measure the TPV for 10wt% to 40wt%；
Measure the polyvinyl resin for 20wt% to 30wt%；
Measure the thermoplastic olefin resin for 30wt% to 50wt%；
Measure the acrylic resin for 1wt% to 10wt%；And
Measure the inorganic filler for 1wt% to 10wt%,
All wt% are based on the gross weight of described resin combination.
A kind of 16. mechanographs, it comprises the resin combination described in claim 1.
A kind of 17. methods for preparing mechanograph, it comprises the following steps:
Obtain TPV and polyvinyl resin from biomass respectively；
By the described TPV for 10wt% to 40wt% for the combined amount, measure as 20
The described polyvinyl resin of wt% to 30wt%, measure thermoplastic olefin for 30wt% to 50wt%
Resin, measure the acrylic resin for 1wt% to 10wt% and measure the nothing for 1wt% to 10wt%
Machine filler is based on the gross weight of described mixture preparing mixture, all wt%；And
Mechanograph is prepared by the step including melting described mixture.
18. methods according to claim 17, wherein, described mixture uses single screw rod
Extruder, double screw extruder, kneader or Banbury mixer are melting.
A kind of 19. vehicles, it comprises the resin combination described in usage right requirement 1 and prepares
Mechanograph.
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| KR10-2015-0099816 | 2015-07-14 | ||
| KR1020150099816A KR101734662B1 (en) | 2015-07-14 | 2015-07-14 | Bio resin composition and bio molded article using the same |
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| KR102333597B1 (en) * | 2020-04-27 | 2021-12-02 | 주식회사 무진 | Eco friendly foam having excellent flame retardant for vehicle seat and manufacturing method thereof |
| KR20220099129A (en) * | 2021-01-04 | 2022-07-13 | 현대자동차주식회사 | Artificial leather for automotive interior materials, and automotive interior materials including the same |
| WO2024025305A1 (en) * | 2022-07-25 | 2024-02-01 | 경상국립대학교 산학협력단 | Thermoplastic vulcanizate comprising bio-polypropylene |
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| KR20170008523A (en) | 2017-01-24 |
| US20170015820A1 (en) | 2017-01-19 |
| KR101734662B1 (en) | 2017-05-11 |
| US9803072B2 (en) | 2017-10-31 |
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